Chen Jin-Rong, Wei Pei-Sin, Ju Yi-Ru, Tsai Sung-Yu, Yen Pei-Yuan, Kao Chien-Han, Wang Yi-Hsuan, Chuang Wei-Tsung, Wu Kuan-Yi
Department of Textile Engineering, University of Chinese Culture University, 55 Hwa-Kang Road, Yang-Ming-Shan, Taipei 11114, Taiwan.
Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu 30010, Taiwan.
ACS Appl Mater Interfaces. 2023 May 17;15(19):23593-23601. doi: 10.1021/acsami.3c01854. Epub 2023 May 8.
Understanding the physicochemical modulation of functional molecules is the primary step in exploring novel stimuli-responsive materials, and preventing the π-π stacking configuration of π-conjugated molecules has been an effective strategy of vapochromic material development, such as of nanoporous frameworks. Nevertheless, the more complicated synthetic strategy should in fact be applied in many circumstances. In this study, we explore a facile supramolecular strategy where the commodity plastic, syndiotactic-poly(methyl methacrylate) (-PMMA), is utilized to wrap C to form the inclusion complex. The structural characterization revealed that Cs in the -PMMA supramolecular helix had a lower coordination number (CN = 2) compared to the face-centered-cubic packing of pure Cs (CN = 12). Since the -PMMA/C helical complex has structural flexibility, the π-π stacking structure of C was further interrupted by the intercalation of toluene vapors, and the complete isolation of C in the complex induced the desired vapochromic behavior. Furthermore, the aromatic interaction between C and aromatic solvent vapors enabled the -PMMA/C inclusion complex to selectively encapsulate chlorobenzene, toluene, etc., and induce the color change. The -PMMA/C inclusion complex exhibited a transparent film of sufficient structural integrity such that it can still induce a reversible color change after several cycles. As a result, a new strategy has been discovered for the development of novel vapochromic materials via host-guest chemistry.
理解功能分子的物理化学调控是探索新型刺激响应材料的首要步骤,而防止π共轭分子的π-π堆积构型一直是开发诸如纳米多孔框架等气致变色材料的有效策略。然而,在许多情况下实际上应采用更复杂的合成策略。在本研究中,我们探索了一种简便的超分子策略,即利用商品塑料间同立构聚(甲基丙烯酸甲酯)(-PMMA)包裹C以形成包合物。结构表征表明,与纯C的面心立方堆积(配位数CN = 12)相比,-PMMA超分子螺旋中的C配位数较低(CN = 2)。由于-PMMA/C螺旋配合物具有结构灵活性,甲苯蒸气的插入进一步破坏了C的π-π堆积结构,并且配合物中C的完全隔离诱导了所需的气致变色行为。此外,C与芳族溶剂蒸气之间的芳族相互作用使-PMMA/C包合物能够选择性地封装氯苯、甲苯等,并引起颜色变化。-PMMA/C包合物表现出具有足够结构完整性的透明薄膜,以至于在几个循环后仍能诱导可逆的颜色变化。因此,通过主客体化学发现了一种开发新型气致变色材料的新策略。